Methods of controlling ziegler-natta pre-catalyst particles formation and use for olefin polymerization

ABSTRACT

A colloidal suspension includes an organic phase and a complex of Formula I as precursor for Ziegler-Natta catalyst synthesis: 
       XTiCl p (OR 1 ) 4-p .YMg(OR 2 ) q (OR 3 ) t    (I).
 
     In Formula I, a molar ratio of X to Y (X/Y) is from 0.2 to 5.0, p is 0 or 1, 0&lt;q&lt;2, 0&lt;t&lt;2, the sum of q and t is 2, R 1 , R 2 , and R 3  are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R 2  is not the same as R 3 .

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. ProvisionalApplication No. 62/898,207, filed Sep. 10, 2019, the contents of whichare incorporated herein by reference in their entirety.

FIELD

The present technology is generally related to polyolefin catalysts.More specifically, the technology is related to Ziegler-Natta catalystsfor the preparation of polyolefins.

BACKGROUND

Ziegler catalysts are widely known and used for a variety of polyolefinproducts. For example, U.S. Pat. No. 4,447,587 describes the preparationof a solid pre-catalyst by dropwise addition of TiCl₄ into a dispersionof magnesium ethylate in diesel oil. The supernatant is washed fourtimes with diesel oil, and the last washing protocol uses diesel oil toobtain the final solid pre-catalyst, which is then activated withtriethylaluminum. U.S. Pat. No. 5,648,309 similarly preparespre-catalysts with the introduction of different transition metals. U.S.Pat. No. 4,972,035 describes the preparation of pre-catalysts fromanhydrous magnesium chloride in decane and 2-ethylhexyl alcohol to forma solution, followed by ethyl benzoate addition. The resulting solutionis then added dropwise to an excess of TiCl₄, followed by heating. Aftertermination of the reaction, a solid portion was collected throughfiltration and washed to obtain a granular pre-catalyst having anaverage particle diameter of 1.0 μm and a particle size distributionthat the geometrical standard deviation was 1.2. U.S. Pat. No. 4,933,393describes the preparation of pre-catalysts by feeding anhydrousmagnesium chloride and hexane into a reactor, adding ethanol,diethylaluminum chloride, and TiCl₄. A solid precipitate is thenseparated by filtering and washed with hexane to obtain the finalpre-catalyst as an agglomerate of fine solid particles of about 1 μm indiameter in a plurality of layers.

In other illustrative pre-catalyst preparations, U.S. Pat. No. 6,545,106describes the preparation of pre-catalysts by preparing magnesiumethylate from magnesium metal with ethanol in the presence of Ti(OBu)₄.In the reaction, the molar ratio of titanium to magnesium is about 2.Following the addition of ethyl benzoate and isobutylaluminum dichloridein hexane, a solid catalytic complex is collected. U.S. Pat. No.6,174,971 describes the preparation of a pre-catalyst from a slurriedmixture of butyl ethyl magnesium, 2-ethylhexanol, and TiCl(OPr^(i))₃(Pr^(i) is isopropyl) in hexane to obtain a clear solution. The solutionmay then be treated with triethylaluminum followed by the addition ofTiCl₄/Ti(OBu₄) (Bu is n-butyl) to form a precipitate that is thencollected. The final pre-catalyst using this recipe includes an extraimpregnation step with TiCl₄ and a pre-contact step withtriethylaluminum. European Patent No 2 081 969 describes the preparationof pre-catalysts from magnesium powder in chlorobenzene with dibutylether, iodine, and butyl chloride, followed by contact with (C₆H₅)SiCl₃and Si(OCH₂CH₃)₄ to form a suspension. TiCl₄ was then added to thesuspension, and a precipitate was collected. U.S. Pat. No. 9,068,025describes the reaction of a solution of dibutyl magnesium withisooctanol to obtain a clear solution. To the solution is added asolution of polystyrene-polybutadiene triblock copolymer, followed bythe addition of BCl₃ and TiCl₄, in sequence, at low temperature. Afterbringing the temperature to 50° C., a precipitated solid is collectedand washed. U.S. Pat. No. 9,587,047 describes the reaction of magnesiumethylate and Ti(OBu)₄ to obtain a clear liquid upon heating. Aftercooling and dilution with hexane to obtain a clear solution, ethylaluminum dichloride (EADC) is added, and the mixture refluxed. Uponcooling, a solid is obtained and washed.

SUMMARY

In one aspect a complex of Formula I is provided:

XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I).

In Formula I, a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0or 1; 0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are eachindependently a linear or branched alkyl, a linear or branchedheteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substitutedheterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R² isnot the same as R³. In some embodiments, R¹ may be a C₃-C₆ alkyl, R² maybe C₂-C₄ alkyl, and R³ may be a C₃-C₆ alkyl. In some embodiments, R¹ maybe n-butyl, R² may be ethyl, and R³ may be n-butyl. In any of the aboveembodiments, p may be 1. In any of the above embodiments, q may be about1 and t may be about 1. In any of the above embodiments, X may be 0.2 to0.5 and Y may be 0.6 to 0.8. In any of the above embodiments, the ratioof X:Y may be from 1 to 3. In any of the above embodiments, the ratio ofX:Y may be about 2.

In any of the above embodiments, the complex may exhibit a ¹³C NMRspectra having an alkoxide resonance from 50 ppm to 80 ppm versusresidual solvent peak of deuterated toluene-d₈. In any of the aboveembodiments, the complex of may exhibit a ¹³C NMR spectra having anaryloxide resonance from 40 ppm to 120 ppm versus residual solvent peakof deuterated toluene-d₈. In any of the above embodiments, a weightresidue obtained by thermal gravimetric analysis (TGA) may be from 20 wt% to 35 wt %. In any of the above embodiments, the complex may exhibit aFourier Transform Infrared C—H stretching vibration at a wavenumber from2500 cm⁻¹ to 4000 cm⁻¹.

In another aspect, a colloidal suspension comprising an organic solventand a complex of Formula I according to any of the above embodiments isprovided. According to any embodiments, the organic solvent may includean alkane, aromatic, or a mixture of any two or more thereof. Forexample, the organic solvent may include n-hexane, n-pentane,cyclohexane, toluene, benzene, benzine, o-cresol, p-cresol, m-cresol,1,2-dimethylbenzene, 1,3-dimethylbenzene, 1,4-dimethylbenzene,ethylbenzene, cumine, trichloroethylene, trichlorobenzene,o-dichlorobenzene, or a mixture of any two or more thereof.

In any of the above embodiments, the complex exhibits a multimodaldomain size of a dispersed phase. In any of the above embodiments, theconcentration of the Ti and Mg may be from 1×10⁻⁵M to 2.0 M, asdetermined by inductively coupled plasma-optical emission spectrometry(ICP-OES). In any of the above embodiments, the multimodal domains mayexhibit a first peak with a domain size mean from 1 nm to 10 nm indiameter, and a second peak with a domain size mean from 250 nm to 350nm in diameter at 20° C. In any of the above embodiments, the multimodaldomain size may exhibit a first peak with a domain size mean from 250 nmto 400 nm in diameter, and a second peak with a domain size mean from4000 nm to 6000 nm in diameter at 50° C. In any of the aboveembodiments, the multimodal domain size may exhibit a first peak whenmeasured by Focus Beam Reflectance Measurement (FBRM) with a cord lengthmean from 1 μm to 10 μm, when measured from −30° C. to 60° C.

In yet another aspect, a solid pre-catalyst system is provided thatincludes solid particles of a composite of a reaction product of ahalogenated compound and any embodiment of the complex of Formula I,including the colloidal suspensions of the complex of Formula I, asdescribed herein. In some embodiments, the halogenated compound includesdiethyl aluminum chloride (DEAC), ethylaluminum sesquichloride (EASC),ethyl aluminum dichloride (EADC), titanium tetrachloride (TiCl₄),silicon tetrachloride (SiCl₄) or a mixture of any two or more thereof.The halogenated compounds may be in an organic solvent as describedabove. For example, the halogenated compound may be present in theorganic solvent from about 1 to about 80 wt %, from about 5 to about 70wt %, from about 25 to 70 wt %, or from about 40 to 60 wt %. In someembodiments, the organic solvent may include pentane, hexane, heptane,octane, and the like. In any of the above embodiments, the Ti may bepresent from 0.5 wt % to 30 wt %, the Mg may be present from 1 wt % to20 wt %, the Al may be present from 1 wt % to 20 wt %, and/or the solidparticles exhibit a D₅₀ from 1 μm to 30 μm. Any of the aboveembodiments, may further include an alternative Lewis acid compound.

In a further aspect, a method of polymerizing or co-polymerizing anolefin monomer is provided, the method including contacting a reducingagent with a solid pre-catalyst system that includes solid particles ofa composite of a reaction product of a halogenated compound and anyembodiment of the colloidal suspension of the complex of Formula I asdescribed herein with at least one olefin monomer. In some embodiments,the olefin monomer may include ethylene, propylene, 1-butene,4-methyl-1-pentene, 1-hexene, 1-octene, or a mixture of any two or morethereof. In any such embodiments, the solid catalyst system may exhibitan activity of greater than 2 kg_(PE)·g_(Cat) ⁻¹h⁻¹. In one embodiment,the olefin may be ethylene, and the method may also include collectingpolyethylene exhibiting a viscosity molecular weight (M_(v)) of greaterthan 1×10⁶ g/mol. In some embodiments, reducing agents include, but arenot limited to, diethyl aluminum chloride (DEAC), triethylaluminum(TEA), ethylaluminum sesquichloride (EASC), ethyl aluminum dichloride(EADC), triisobutyl aluminum (TiBA), trimethyl aluminum (TMA),methylaluminoxane (MAO), or a mixture of any two or more thereof.

In a further aspect, a method of polymerizing or co-polymerizing anolefin monomer in presence of a chain transfer agent, such as hydrogenis provided, the method including contacting a reducing agent with asolid pre-catalyst system that includes solid particles of a compositeof a reaction product of a halogenated compound and any embodiment ofthe colloidal suspension of the complex of Formula I as described hereinwith at least one olefin monomer. In some embodiments, the olefinmonomer may include ethylene, propylene, 1-butene, 4-methyl-1-pentene,1-hexene, 1-octene, or a mixture of any two or more thereof. In any suchembodiments, the solid catalyst system may exhibit an activity ofgreater than 2 kg_(PE)·g_(Cat) ⁻¹h⁻¹. In one embodiment, the olefin maybe ethylene, and the method may also include collecting polyethyleneexhibiting a number average molecular weight (M_(n)) of greater than1×10⁴ g/mol, a weight average molecular weight (M_(w)) of greater than1.5×10⁵ g/mol. The obtained polymers can also be fractionated bycrystallization elution fractionation (CEF) technique, which less than 5wt % of the polymer will be eluted with 1,2-dichloribenzene under 30° C.(X_(Tel<30)° C.^(A)) and more than 90 wt % of the polymer will eluteabove 90° C. (X_(Tel>85)° C.^(B)). In some embodiments, reducing agentsinclude, but are not limited to, diethyl aluminum chloride (DEAC),triethylaluminum (TEA), ethylaluminum sesquichloride (EASC), ethylaluminum dichloride.

In yet a further aspect, a method of forming a pre-catalyst precursor isprovided, the method including contacting a titanium compound of FormulaTi(OR²⁰)₄ with TiCl₄ to form a reactive mixture; adding an alcohol offormula R²⁰OH to the reactive mixture to form a second mixture; adding amagnesium compound of Formula Mg(OR²¹)₂ to the second mixture to form athird mixture having a molar ratio of titanium compound to magnesiumcompound of 0.2 to 5.0; and heating the third mixture to form acolloidal suspension of the complex of Formula I, as described herein.

In yet a further aspect, a method to prepare a solid pre-catalyst systemincludes the reaction of the colloidal suspension comprising an organicsolvent and a complex of Formula I with a halogenated compound or amixture of halogenated compounds.

In yet a further aspect, a method to prepare a solid pre-catalyst systemincludes adding the halogenated compound or a mixture of the halogenatedcompound into the colloidal suspension comprising an organic solvent anda complex of Formula I under controlled flow rate, temperature,concentration, and/or stirring speed.

In yet a further aspect, a method to prepare a solid pre-catalyst systemincludes adding the colloidal suspension comprising an organic solventand a complex of Formula I into the halogenated compound or a mixture ofthe halogenated compound under controlled flow rate, temperature,concentration, and/or stirring speed.

In yet a further aspect, a method to prepare a solid pre-catalyst systemincludes adding simultaneously the halogenated compound or a mixture ofthe halogenated compound and the colloidal suspension comprising anorganic solvent and a complex of Formula I into an inert liquid mediumunder controlled flow rate, temperature, concentration, and/or stirringspeed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a ¹³C NMR spectra of samples of Example 3.

FIG. 2 is the Fourier Transform Infrared (FTIR) spectra of Example 3,Ti(OBu)₄, and Mg(EtO)₂.

FIG. 3 is a graph of the measurement of the unweighted cord lengthmedian of a suspension of Example 1 in hexane.

FIG. 4 is a graph of cord length unweighted median under stirringconditions (up to 400 rpm), concentration of [Ti] between 0.076-0.293mol/L and temperature of 30° C. or 40° C., according to the Example 1.

FIG. 5 is a graph of DLS results for Examples 1-3 samples under the sameconditions, and which display a similar bimodal intensity distributionat 25° C.

FIG. 6 is a graph illustrating the effect of reaction temperature onpre-catalyst particle size, according to the Examples.

FIG. 7 is a graph of the concentration of titanium species relative tothe Ti—Mg complex consumption and pre-catalyst formation over reactiontime assuming immediate conversion of the reactants, according to theExamples.

FIG. 8 is a graph illustrating the effect of Ti—Mg complex concentrationon the pre-catalyst particle size, according to the Examples.

FIG. 9 includes illustrations regarding how the terms solution,colloidal solution, suspension, and colloidal suspension are used in thepresent application.

FIGS. 10A and 10B are illustrations of different reactor setups forformation of the pre-catalysts described herein.

FIG. 11 is a graph of particle size (D₅₀) as a function of stirringrate, according to the examples.

FIGS. 12A and 12B are plots of CE of polymerization performed withcatalyst systems prepared in Examples 13 and 14 under differentactivation conditions, according to the polymerization conditionsdescribed in Example 22.

FIG. 13 is a graph of a particle size distribution measured in aMastersizer 2000 laser diffraction particle size analyzer from MalvernPanalytical, according to the examples.

FIG. 14 includes illustrations of different reactor setups for formationof the pre-catalysts described herein.

FIG. 15 is a graph of particles size peak mode versus temperature forfeeding methods B and C.

FIG. 16 is a graph of the turbidity image analysis, according to theExamples.

FIG. 17 is a graph of the turbidity unity that was modeled with respectto time where k_(T)(T) is the TU time constant and is a function ofreactor operating temperature, and TU_(max)(T) is the maximum TU for thesystem, and it is also a function of reactor temperature, according tothe Examples.

DETAILED DESCRIPTION

Various embodiments are described hereinafter. It should be noted thatthe specific embodiments are not intended as an exhaustive descriptionor as a limitation to the broader aspects discussed herein. One aspectdescribed in conjunction with a particular embodiment is not necessarilylimited to that embodiment and may be practiced with any otherembodiment(s).

As used herein, “about” will be understood by persons of ordinary skillin the art and will vary to some extent depending upon the context inwhich it is used. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “about” will mean up to plus or minus 10% of the particular term.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the elements (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. Recitation of ranges of values herein are merely intended toserve as a shorthand method of referring individually to each separatevalue falling within the range, unless otherwise indicated herein, andeach separate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein may beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the embodiments and does not pose alimitation on the scope of the claims unless otherwise stated. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential.

As used herein, the term “solution” refers to a liquid or solid phasecontaining more than one substance, when for convenience one (or more)substance, which is called the solvent, is treated differently from theother substances, which are called solutes. In such mixture the soluteis stabilized by the solvent or simply solvated, as a result the solutemay be present in a particle size of 1 nm, or less, in the largestdimension.

As used herein, the term “colloidal solution” refers to a system inwhich a substance or a mixture of substances form particles or domainswhich are regularly dispersed in a continuous phase of a differentcomposition. In such system, the particles or domains have a size offrom 1 nm to 100 nm in the largest dimension.

As used herein, the term “suspension” refers to a system in which asubstance or a mixture of substances form particles or domains whiledispersed in a continuous phase of a different composition (or state)having a size of greater than 100 nm in the largest dimension. At thissize level aggregation of the individual particles of the material maystart to form and precipitate out as sediment without the presence ofany means of agitation. The particles or domains may or may notaggregate and disperse regularly in the continuous phase to form acolloidal suspension which does not precipitate or sediment without thepresence of any means of agitation. Colloidal suspensions may havedomains or particle sizes of from greater than 100 nm to 10 μm.Solutions, colloidal solutions, and suspensions are illustrated in FIG.9.

In general, “substituted” refers to an alkyl, alkenyl, aryl, or ethergroup, as defined below (e.g., an alkyl group) in which one or morebonds to a hydrogen atom contained therein are replaced by a bond tonon-hydrogen or non-carbon atoms. Substituted groups also include groupsin which one or more bonds to a carbon(s) or hydrogen(s) atom arereplaced by one or more bonds, including double or triple bonds, to aheteroatom. Thus, a substituted group will be substituted with one ormore substituents, unless otherwise specified. In some embodiments, asubstituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents.Examples of substituent groups include: halogens (i.e., F, Cl, Br, andI); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy,heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo);carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines;aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls;sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones;azides; amides; ureas; amidines; guanidines; enamines; imides;isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitrogroups; nitriles (i.e., CN); and the like.

The definition of further substituted is expanded to also includealkylation or arylation of the underlying alkyl, aryl, heteroaryl,heterocyclyl, or cyclyl groups. This means that, e.g. an aryl group mayalso include alkyl groups, aryl groups, fused ring structures, and thelike. This also means that general reference to the aryl group, e.g.“phenyl,” includes tolyl, tert-butyl, di-tert-butyl, bi-phenyl,anthracenyl, and the like.

As used herein, “alkyl” groups include straight chain and branched alkylgroups having from 1 to about 20 carbon atoms, and typically from 1 to12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Alkylgroups may be substituted or unsubstituted. An alkyl group may besubstituted one or more times. An alkyl group may be substituted two ormore times. Examples of straight chain alkyl groups include methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octylgroups. Examples of branched alkyl groups include, but are not limitedto, isopropyl, sec-butyl, t-butyl, neopentyl, isopentyl groups, and1-cyclopentyl-4-methylpentyl. Representative substituted alkyl groupsmay be substituted one or more times with, for example, amino, thio,hydroxy, cyano, alkoxy, and/or halo groups such as F, Cl, Br, and Igroups. As used herein the term haloalkyl is an alkyl group having oneor more halo groups. In some embodiments, haloalkyl refers to aper-haloalkyl group. Heteroalkyl groups are alkyl groups containing aheteroatom.

Cycloalkyl groups are cyclic alkyl groups such as, but not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, andcyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8ring members, whereas in other embodiments the number of ring carbonatoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substitutedor unsubstituted. Cycloalkyl groups further include polycycliccycloalkyl groups such as, but not limited to, norbornyl, adamantyl,bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused ringssuch as, but not limited to, decalinyl, and the like. Cycloalkyl groupsalso include rings that may further have straight or branched chainalkyl groups bonded thereto as defined above. Representative substitutedcycloalkyl groups may be mono-substituted or substituted more than once,such as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substitutednorbornyl or cycloheptyl groups, which may be substituted with, forexample, alkyl, alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.

Alkenyl groups are straight chain, branched or cyclic alkyl groupshaving 2 to about 20 carbon atoms, and further including at least onedouble bond. In some embodiments alkenyl groups have from 1 to 12carbons, or, typically, from 1 to 8 carbon atoms. Alkenyl groups may besubstituted or unsubstituted. Alkenyl groups include, for instance,vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl,cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienylgroups among others. Alkenyl groups may be substituted similarly toalkyl groups. Divalent alkenyl groups, i.e., alkenyl groups with twopoints of attachment, include, but are not limited to,

CH—CH═CH₂,

C═CH₂, or

C═CHCH₃.

As used herein, “aryl”, or “aromatic,” groups are cyclic aromatichydrocarbons that do not contain heteroatoms. Aryl groups includemonocyclic, bicyclic, and polycyclic ring systems. Thus, aryl groupsinclude, but are not limited to, phenyl, azulenyl, heptalenyl,biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl,pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl,indanyl, pentalenyl, and naphthyl groups. An aryl group with one or morealkyl groups may also be referred to as alkaryl groups. In someembodiments, aryl groups contain 6-14 carbons, and in others from 6 to12 or even 6-10 carbon atoms in the ring portions of the groups. Thephrase “aryl groups” includes groups containing fused rings, such asfused aromatic-aliphatic ring systems (e.g., indanyl,tetrahydronaphthyl, and the like). Aryl groups may be substituted orunsubstituted.

Heterocyclyl or heterocycle refers to both aromatic and nonaromatic ringcompounds including monocyclic, bicyclic, and polycyclic ring compoundscontaining 3 or more ring members of which one or more is a heteroatomsuch as, but not limited to, N, O, and S. Examples of heterocyclylgroups include, but are not limited to: unsaturated 3 to 8 memberedrings containing 1 to 4 nitrogen atoms such as, but not limited topyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridinyl,dihydropyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl (e.g.4H-1,2,4-triazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl etc.),tetrazolyl, (e.g. 1H-tetrazolyl, 2H tetrazolyl, etc.); saturated 3 to 8membered rings containing 1 to 4 nitrogen atoms such as, but not limitedto, pyrrolidinyl, imidazolidinyl, piperidinyl, piperazinyl; condensedunsaturated heterocyclic groups containing 1 to 4 nitrogen atoms suchas, but not limited to, indolyl, isoindolyl, indolinyl, indolizinyl,benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl;unsaturated 3 to 8 membered rings containing 1 to 2 oxygen atoms and 1to 3 nitrogen atoms such as, but not limited to, oxazolyl, isoxazolyl,oxadiazolyl (e.g. 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl,1,2,5-oxadiazolyl, etc.); saturated 3 to 8 membered rings containing 1to 2 oxygen atoms and 1 to 3 nitrogen atoms such as, but not limited to,morpholinyl; unsaturated condensed heterocyclic groups containing 1 to 2oxygen atoms and 1 to 3 nitrogen atoms, for example, benzoxazolyl,benzoxadiazolyl, benzoxazinyl (e.g. 2H-1,4-benzoxazinyl etc.);unsaturated 3 to 8 membered rings containing 1 to 3 sulfur atoms and 1to 3 nitrogen atoms such as, but not limited to, thiazolyl,isothiazolyl, thiadiazolyl (e.g. 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl,1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, etc.); saturated 3 to 8 memberedrings containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms such as,but not limited to, thiazolodinyl; saturated and unsaturated 3 to 8membered rings containing 1 to 2 sulfur atoms such as, but not limitedto, thienyl, dihydrodithiinyl, dihydrodithionyl, tetrahydrothiophene,tetrahydrothiopyran; unsaturated condensed heterocyclic rings containing1 to 2 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limitedto, benzothiazolyl, benzothiadiazolyl, benzothiazinyl (e.g.2H-1,4-benzothiazinyl, etc.), dihydrobenzothiazinyl (e.g.2H-3,4-dihydrobenzothiazinyl, etc.), unsaturated 3 to 8 membered ringscontaining oxygen atoms such as, but not limited to furyl; unsaturatedcondensed heterocyclic rings containing 1 to 2 oxygen atoms such asbenzodioxolyl (e.g., 1,3-benzodioxoyl, etc.); unsaturated 3 to 8membered rings containing an oxygen atom and 1 to 2 sulfur atoms suchas, but not limited to, dihydrooxathiinyl; saturated 3 to 8 memberedrings containing 1 to 2 oxygen atoms and 1 to 2 sulfur atoms such as1,4-oxathiane; unsaturated condensed rings containing 1 to 2 sulfuratoms such as benzothienyl, benzodithiinyl; and unsaturated condensedheterocyclic rings containing an oxygen atom and 1 to 2 oxygen atomssuch as benzoxathiinyl. Heterocyclyl group also include those describedabove in which one or more S atoms in the ring is double-bonded to oneor two oxygen atoms (sulfoxides and sulfones). For example, heterocyclylgroups include tetrahydrothiophene oxide and tetrahydrothiophene1,1-dioxide. Typical heterocyclyl groups contain 5 or 6 ring members.Thus, for example, heterocyclyl groups include morpholinyl, piperazinyl,piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl,1,2,4-triazolyl, tetrazolyl, thiophenyl, thiomorpholinyl,thiomorpholinyl in which the S atom of the thiomorpholinyl is bonded toone or more O atoms, pyrrolyl, pyridinyl, homopiperazinyl,oxazolidin-2-onyl, pyrrolidin-2-onyl, oxazolyl, quinuclidinyl,thiazolyl, isoxazolyl, furanyl, dibenzylfuranyl, and tetrahydrofuranyl.Heterocyclyl or heterocycles may be substituted.

Heteroaryl groups are aromatic ring compounds containing 5 or more ringmembers, of which, one or more is a heteroatom such as, but not limitedto, N, O, and S. Heteroaryl groups include, but are not limited to,groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl,isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl,thiophenyl, benzothiophenyl, furanyl, benzofuranyl, dibenzofuranyl,indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl,imidazopyridinyl (azabenzimidazolyl), pyrazolopyridinyl,triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl,benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl,purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl,tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroarylgroups include fused ring compounds in which all rings are aromatic suchas indolyl groups and include fused ring compounds in which only one ofthe rings is aromatic, such as 2,3-dihydro indolyl groups. Although thephrase “heteroaryl groups” includes fused ring compounds, the phrasedoes not include heteroaryl groups that have other groups bonded to oneof the ring members, such as alkyl groups. Rather, heteroaryl groupswith such substitution are referred to as “substituted heteroarylgroups.” Representative substituted heteroaryl groups may be substitutedone or more times with various substituents such as those listed above.

As used herein, the prefix “halo” refers to a halogen (i.e. F, Cl, Br,or I) being attached to the group being modified by the “halo” prefix.For example, haloaryls are halogenated aryl groups.

Groups described herein having two or more points of attachment (i.e.,divalent, trivalent, or polyvalent) within the compound of the presenttechnology are designated by use of the suffix, “ene.” For example,divalent alkyl groups are alkylene groups, divalent aryl groups arearylene groups, divalent heteroaryl groups are divalent heteroarylenegroups, and so forth.

It has now been surprisingly found that stable, colloidal suspensions ofa Ti—Mg complex of Formula I (XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)(I)) may be formed and used as reactant to the preparation of anefficient Ziegler-Natta catalysts for olefin polymerization reactions.The control in the composition of the Ti—Mg complex enables productionof a colloidal suspension with domains and aggregates. Without beingbound by theory, the aggregation and breakage of the domains appears tobe driven by the surface tension of the liquid droplets, the size ofwhich may be influenced by stirring speed, concentration, temperature,solvent medium, and the chemical composition. Therefore, the control ofthe dimension of the particles dispersed in the continuous phase, whichseems to act as a nucleation domain during the pre-catalyst formation,controls the pre-catalyst particle composition and characteristics.Provided herein are the compositions, methods of making the colloidalsuspensions, method of making the pre-catalysts from the colloidalsuspensions, and methods of using the catalyst system in the preparationof polyolefins.

Furthermore, it has been observed that the particle size of the catalystsystem may be controlled by changing the addition order of thereactants. For example, by adding the halogenated compound to acolloidal suspension of a Ti—Mg complex of Formula I, compared tosimultaneously adding the colloidal suspension of a Ti—Mg complex ofFormula I and the halogenated compound into an inert medium, results inat least a doubling of the D₅₀ particle size of the obtained solidpre-catalyst particles when the stirring rate is the same. Two of theaddition methods are exemplified in FIG. 10A and FIG. 10B. Methods ofpreparation are further described below.

In Formula I, a molar ratio of X:Y is 0.2 to 5.0, p is 0 or 1, 0<q<2,0<t<2, the sum of q and t is 2, R¹, R², and R³ are each independently alinear or branched alkyl, a linear or branched heteroalkyl, acycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, asubstituted aryl, or a (heteroaryl)alkyl; and R² is not the same as R³.In some embodiments, R¹ may be a C₃-C₆ alkyl, R² may be C₂-C₄ alkyl, andR³ may be a C₃-C₆ alkyl. One illustrative and non-limiting embodimentincludes where R¹ is n-butyl, R² is ethyl, and R³ is n-butyl. In someembodiments of Formula I, p is 1. In any such embodiments, q may beabout 1 and t may be about 1. In some embodiments, Xis from 0.2 to 0.5and Y is from 0.6 to 0.8. The ratio of X:Y may vary, as noted above. Forexample, the ratio of X:Y may be from 1 to 3, or about 2.

In a carbon-13 nuclear magnetic resonance (¹³C NMR) of the suspendedcomplex of Formula I in hexane and the isolated complex of Formula I, analkoxide resonance from 50 ppm to 80 ppm versus residual solvent signalof deuterated toluene-d₈ is exhibited (FIG. 1). This is indicative ofthe mixture of alkoxy groups derived from the Ti—Mg complex. In someembodiments, where the complex of Formula I include an aryloxide group,a ¹³C NMR spectra of the complex may exhibit a resonance from 40 ppm to120 ppm versus residual solvent signal of deutareted toluene-d₈.

Thermal gravimetric analysis (TGA) may be used to support thecharacterization of the compounds by comparing actual to theoreticalweight loss from a sample of the complex. In the case of the complexesof Formula I, after TGA, the weight residue obtained may be from 20 wt %to 35 wt %.

Like ¹³C NMR and TGA, Fourier Transform Infrared (FTIR) spectroscopy maybe used to characterize the complexes. In the compositions of Formula I,the C—H stretch vibration derived from metal-oxygen-C—H may be observedusing FTIR at a wavenumber from 2500 cm⁻¹ to 4000 cm⁻¹.

The colloidal suspension of the complex of Formula I may also include anorganic phase. For example, the organic phase may be an alkane,aromatic, or a mixture of any two or more thereof. Illustrative examplesof the organic phase include, but are not limited to, n-hexane,n-pentane, cyclohexane, toluene, benzene, benzine, o-cresol, p-cresol,m-cresol, 1,2-dimethylbenzene, 1,3-dimethylbenzene, 1,4-dimethylbenzene,ethylbenzene, cumine, trichloroethylene, trichlorobenzene,o-dichlorobenzene, or a mixture of any two or more thereof.

Interestingly, the complexes/colloidal suspensions of the complexesdescribed herein, exhibit a multimodal domain size of a dispersed phase.As used herein a “dispersed phase” is the particles or domains that areof interest which have essentially the properties of a bulk phase of thesame composition, while the “continuous” phase is different incomposition. In the dispersed phase, the multimodal domain size a firstpeak with a domain size mean from 1 nm to 10 nm in diameter, and asecond peak with a domain size mean from 250 nm to 350 nm in diameter at20° C. This includes a multimodal domain size exhibiting a first peakwith a domain size mean from 250 nm to 400 nm in diameter, and a secondpeak with a domain size mean from 4000 nm to 6000 nm in diameter at 50°C.

ICP-OES may be used to determine the Ti and Mg concentrations in thecompound of Formula I. In some embodiments, the concentration of the Tiand Mg was determined by ICP-OES to be from 1×10⁻⁵M to 2.0 M, asdetermined by ICP-OES.

One technique for determining the particle size of the complex ofFormula I, FBRM. According to FBRM, the complexes and colloidalsuspensions may exhibits a first peak with a cord length mean from 1 μmto 10 μm, when measured from −30° C. to 60° C.

In another embodiment, a solid pre-catalyst system is formed from thecolloidal suspension of compound of Formula I as described above, and ahalogenated compound. In Formula I(XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)), a molar ratio of X to Y(X/Y) is from 0.2 to 5.0; p is 0 or 1; 0<q<2; 0<t<2; the sum of q and tis 2; R¹, R², and R³ are each independently a linear or branched alkyl,a linear or branched heteroalkyl, a cycloalkyl, a substitutedcycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a(heteroaryl)alkyl; and R² is not the same as R³. The halogenatedcompound may be a Lewis acid compound. Illustrative Lewis acid compoundsmay include one or more of diethyl aluminum chloride (DEAC),ethylaluminum sesquichloride (EASC), ethyl aluminum dichloride (EADC),titanium tetrachloride (TiCl₄), and silicon tetrachloride (SiCl₄). Inthe solid pre-catalyst system, the total amount of Ti may be from about0.5 wt % to about 30 wt %. In the solid pre-catalyst system, the Mg maybe present from about 1 wt % to about 20 wt %. In the solid pre-catalystsystem, the Al may be present from about 1 wt % to about 20 wt %. In thesolid pre-catalyst system, the solid particles exhibit a D₅₀ from 1 μmto 30 μm if the reaction is carried out with the addition method A (FIG.10A) and a D₅₀ from 1 μm to 15 μm if the reaction is carried out withthe addition method B (FIG. 10B) under similar reaction conditions.

In any of the above embodiments, the solid pre-catalyst system mayinclude a reducing agent. Illustrative reducing agents include, but arenot limited to, diethyl aluminum chloride (DEAC), triethylaluminum(TEA), ethylaluminum sesquichloride (EASC), ethyl aluminum dichloride(EADC), triisobutyl aluminum (TiBA), trimethyl aluminum (TMA),methylaluminoxane (MAO), or a mixture of any two or more thereof.

The Ziegler-Natta catalyst systems produced from colloidal suspensionsthat are described herein may be used as polymerization- orco-polymerization-catalysts for the polymerization of olefins.Accordingly, methods of using any of the pre-catalyst systems producedfrom the colloidal suspension in a method of polymerization areprovided. The methods may include contacting a reducing agent with asolid pre-catalyst system that includes solid particles of a compositeof a reaction product of a halogenated compound and a colloidalsuspension of complex of Formula I(XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)) as embodied herein with atleast one olefin monomer. A wide variety of olefins may be polymerizedwith the catalysts. Illustrative, non-limiting, olefins may includeethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene,or a mixture of any two or more thereof.

The catalyst efficiency (“CE”) of the solid catalyst systems has beendetermined to be greater than 2 kg_(PE)·g_(Cat) ⁻¹·h⁻¹. This may includefrom 2 kg_(PE)·g_(Cat) ⁻¹·h⁻¹ to 50 kg_(PE)·g_(Cat) ¹·h⁻¹, and from 4kg_(PE)·g_(Cat) ⁻¹·h⁻¹ to 20 kg_(PE)·g_(Cat) ⁻¹·h⁻¹.

In some embodiments of the methods, the olefin may be ethylene, and thepolyethylene obtained from the method exhibits an intrinsic viscosity ofgreater than 1.0 dl/g. This may include from 1 dl/g to 50 dl/g, and from5 dl/g to 40 dl/g.

In another aspect, methods of forming a pre-catalyst composition thatincludes the complex of Formula I are provided. The methods includecontacting a titanium compound of Formula Ti(OR²⁰)₄ with TiCl₄ to form areactive mixture. Alcohol of formula R²⁰OH may then be added to thereactive mixture to form a second mixture. To the second mixture is thenadded a magnesium compound of Formula Mg(OR²¹)₂ to form a third mixturehaving a molar ratio of titanium compound to magnesium compound of 0.2to 5.0. Finally, the third mixture is heated to form a complex ofFormula I, as described herein, followed by the removal of ethanol as aby-product of this reaction.

In the methods of forming, formation of the reactive mixture mayconducted at, or below about ambient temperature to minimize or preventexothermic runaway. An illustrative temperature is from about 0° C. to40° C., from about 10° C. to about 40° C., or about 25° C. to about 30°C. Also, the heating of the third mixture is done at a temperaturesufficient for the reaction to proceed and to distill the byproductalcohol from the reaction mixture. While this temperature may vary, itis generally from about 80° C. to about 180° C. In some embodiments, thetemperature is from about 100° C. to 160° C.

As an illustrative example of the method of preparation, the reactivemixture is formed by dropwise addition of TiCl₄ to neat Ti(OBu)₄ at atemperature below 30° C. with stirring and in a molar ratio ofTi(OBu)₄/TiCl₄ of about 3. In this case the TiCl₄ acts as chlorinatingagent to the Ti(OBu)₄, producing TiCl(OBu)₃ through aradical-interexchange reaction. To this titanium compound, under aninert atmosphere and with stirring, magnesium ethoxide powder is addedat molar ratio to the Ti species of 2. The mixture is then heated to130° C. with stirring until the reaction is complete (from about 4 to 6hours). In this step, different amounts of butanol are added resultingin a partial or completed exchange reaction with magnesium ethoxide toform magnesium butoxide or a mixture of magnesium ethoxide and butoxideallowing the formation of a clear liquid. The byproduct of this reaction(ethanol) is collected by Dean-Stark trapping. The temperature is thendecreased to 100° C. and the complex is suspended in hexane to obtain acolloidal suspension with titanium concentration lower than 0.4 mol/L.During the addition of hexane the temperature is allowed to reach 60°C., where it is maintained with stirring for at least 1 hour. Afterward,the colloidal suspension is stable at room temperature.

In further aspects, the methods of preparing a solid pre-catalyst systemas a polyolefin catalyst are dependent upon the reaction conditions andhow the colloidal suspension is prepared. For example, in someembodiments, the method of preparing the solid pre-catalyst systemincludes reacting a colloidal suspension of an organic solvent and acomplex of Formula I with a halogenated compound or a mixture ofhalogenated compounds. In the methods, the complex of Formula I is asdescribed for any embodiment herein. In other embodiments, the method ofpreparing a solid pre-catalyst system includes adding a halogenatedcompound or a mixture of the halogenated compound into a colloidalsuspension that includes an organic solvent and a complex of Formula I,under controlled flow rate, temperature, concentration, and/or stirringspeed. In further embodiments, a method of preparing a solidpre-catalyst system includes adding, simultaneously, a halogenatedcompound (or a mixture of halogenated compounds) and a colloidalsuspension that includes an organic solvent and a complex of Formula I,into an inert liquid medium under controlled flow rate, temperature,concentration, and/or stirring speed.

In the methods, the compound of Formula I, the organic solvents, thecolloidal suspensions, the halogenated compound(s), and the pre-catalystsystems are as described above. However, as noted, reaction conditionssuch as temperature, concentrations, and/or stirring speeds impact theparticle size of the domains in the colloidal suspension and the solidpre-catalyst particles. As shown in FIG. 11, increasing the stirringspeed from 500 to 1750 rpm decreases the D₅₀ value of the particle sizeof the pre-catalyst. In some embodiments, the stirring rate in themethod is from 50 to 3000 rpm, 200 to 2500 rpm, from 400 to 2000 rpm, orfrom 500 to 1800 rpm.

Generally, reactive precipitation processes involving chemical reactionslead to a simultaneous and fast occurrence of nucleation, crystal growthand aggregation. Thus, it may be expected that reaction conditions, suchas temperature and concentration in addition to the stirring speed, mayalso influence the mechanisms of particle formation. As illustrated byFIG. 5, the lower is the temperature of the medium the smaller is thedomain size in the Ti—Mg complex colloidal suspension, which couldsuggest better control of the nucleation domains in a reactiveprecipitation process. It is also known that lower temperature in thereaction medium promotes mechanisms of nucleation and crystal growth,which may result in the formation a smaller pre-catalyst particle sizes,as shown in FIG. 06. On the other hand, as particles are formed,concerns on the increase surface tension in a slurry system should alsobe taken in account due to the increase of cohesive forces. As shown inFIG. 13, the significant increase of the surface tension at the lowestreaction temperature suggests an important contribution from theaggregation mechanisms that broadens the particle size distribution. Thecontrary was observed for diluted reaction mediums due to thesuppression of cohesive forces throughout the particle formation.

In the above methods, the organic solvent and/or inert liquid medium mayindividually include, but is not limited to, an alkane, aromatic, or amixture of any two or more thereof. Illustrative organic solvent and/orinert liquid medium may individually include n-hexane, n-pentane,cyclohexane, toluene, benzene, benzine, o-cresol, p-cresol, m-cresol,1,2-dimethylbenzene, 1,3-dimethylbenzene, 1,4-dimethylbenzene,ethylbenzene, cumine, trichloroethylene, trichlorobenzene,o-dichlorobenzene, or a mixture of any two or more thereof.

In the methods, the halogenated compound(s) may include, but is notlimited to, diethyl aluminum chloride (DEAC), ethylaluminumsesquichloride (EASC), ethyl aluminum dichloride (EADC), titaniumtetrachloride (TiCl₄), silicon tetrachloride (SiCl₄) or a mixture of anytwo or more thereof. In the methods, the halogenated compounds may bediluted in an organic solvent, such as those listed herein, in anyembodiment. The concentration of the halogenated compound at additionmay be in excess of about 5 wt %.

In the above methods, a concentration of the Ti and Mg in the colloidalsuspension is from about 1×10⁻⁵M to about 2.0 M, as determined byICP-OES.

In any of the embodiments herein, the methods may be conducted at atemperature from about −40° C. to +60° C. In any of the embodimentsherein, the methods include a simultaneously feed of the halogenatedcompound and the colloidal suspension of a complex of Formula I atconstant chloride to -OR' molar ratio, where x merely indicates the R¹,R², and R³ groups collectively. In some embodiments the chloride to−OR^(x) molar ratio is from about 0.1 to about 10.

In any of the embodiments herein, the resulting solid pre-catalyst fromthe method exhibits a Ti content from 0.5 wt % to 30 wt %, a Mg contentfrom 1 wt % to 20 wt %, and/or an Al content from 1 wt % to 20 wt %. Thesolid pre-catalyst particles obtained from the method may exhibit a D₅₀from about 1 μm to about 15 μm.

In any of the embodiments herein, the method may further includecontacting the solid pre-catalyst system with a reducing agent.Illustrative reducing agents include, but are not limited to, diethylaluminum chloride (DEAC), triethyl aluminum (TEA), ethylaluminumsesquichloride (EASC), ethyl aluminum dichloride (EADC), triisobutylaluminum (TiBA), trimethyl aluminum (TMA), methylaluminoxane (MAO), or amixture of any two or more thereof. In some embodiments, the solidpre-catalyst system may be further contacted with a reducing agentresulting in a solid catalyst system.

The present invention, thus generally described, will be understood morereadily by reference to the following examples, which are provided byway of illustration and are not intended to be limiting of the presentinvention.

EXAMPLES Example 1

Preparation of a colloidal suspension. Step 1: Ti(OBu)₄ (89.1 mL; 0.27mol) was introduced to a 3 L glass reactor equipped with an overheadstirrer, a Dean-Stark trap, and a reflux condenser under an inertatmosphere at 30° C. The reaction was followed by a dropwise addition ofTiCl₄ (9.61 mL; 0.085 mol) while stirring at 250 rpm and maintaining thetemperature under 30° C. to form a reactive mixture. Step 2: Thereactive mixture was kept under these conditions for one hour, and thenanhydrous n-butanol (31.0 mL, 0.34 mol) was introduced at a flow rate of15 mL/min.¹ Following completion of the n-butanol addition,Mg(OEt)_(2(s)) (77.5g, 0.68 mol) was slowly added under nitrogen. Step3: The reaction temperature was raised to 130° C. and the stirring speedto 500 rpm. This condition was maintained for 1.5 hours, followed by thecollection of by-products (i.e., ethanol) via the Dean-Stark trap.Additional anhydrous n-butanol (25.0 mL, 0.27 mol) was introduced at aflow rate of 15 mL/min, and the reaction was kept under the sameconditions for an additional 3.0 hours. Step 4: The reaction temperaturewas lowered to 100° C. with a stirring speed of 250 rpm, and theDean-Stark trap was removed under nitrogen. The temperature was set to60° C. at the same time n-hexane (2.5 L) was added at a flow rate of 25mL/min. After the addition of hexane was complete, the intermediatecomplex (IC) suspension was maintained at room temperature. ¹ Anhydrousbutanol is prepared by was purchased from Aldrich as an anhydrous1-butanol assay of 99.8%, which was then treated with 3A molecularsieves for further removal of water.

The intermediate complex suspension was determined by ICP-OES to contain0.296 M titanium and 0.618 M magnesium, which is a magnesium:titaniumratio of about 2.1. A combined 41 mL of ethanol (26 mL) and n-butanol(15 mL) were removed via the Dean-Stark trap. This amounts of ethanoland butanol were determined using ¹³C NMR. Assuming complete removal ofethanol, the resultant Ti—Mg complex may have a formula of 0.36TiCl(OBu)₃.0.72 Mg(OEt)_(1.4)(OBu)_(0.6). After collection of the solidsand drying, ICP-OES analysis indicated that it contained 6.39 wt % Tiand 6.56 wt % Mg, with theoretical amounts of 8.46 and 8.60,respectively. The balance of the solids is the alkoxides and halides.The FTIR spectra of the complex of Example 1 and Ti(OBu)₄ were obtainedand the spectra show characteristic α-C—H stretch vibrations bond to Mgand Ti, suggesting the formation of the Ti—Mg complex.

Discussion of Example 1. In this analysis, the integral ratio betweenthe alpha carbons of ethanol and butanol, assigned as C(b) and C(f),respectively, was used as the reference peaks. This result indicates themolar ratio between ethanol and butanol in the collected sample. Byapplying equation (1) is possible to estimate that approximately 26 mLof the collected sample was ethanol. Thus, assuming that most of theethanol produced in step 2 reaction was collected, as shown in Scheme 1,it results in a molar conversion of 0.31 of the butanol-magnesiumethoxide exchange reaction.

$\begin{matrix}{\frac{\int\alpha_{c\; 2}}{\int\alpha_{c\; 4}} = \frac{\frac{\left( {V_{t} - {Vc}_{4}} \right) \cdot \rho_{c\; 2}}{\overset{\_}{M_{c\; 2}}}}{\frac{V_{c\; 2} \cdot \rho_{c\; 4}}{\overset{\_}{M_{c\; 4}}}}} & {{Equation}\mspace{14mu} (1)}\end{matrix}$

Where, ∫α_(c2 & c4) are the ¹³C NMR integral of the alpha carbon peaks,ρ_(c2 & C4) are the densities and M_(c4 & c2) are the molar masses ofethanol and butanol, respectively, V_(t) is the total volume collectedin the Dean-Stark, Vc4 is the volume of butanol. Based on thisinformation, it is possible to estimate the complex composition of Step2 in Example 1, as shown in Scheme 2. Based upon the foregoing, theintermediate complex of Example 1 is:

0.36TiCl(O-n-Bu)₃.0.72Mg(O-Et)_(1.4)(O-n-Bu)_(0.6).

The chemical formula isC_(8.06)H_(18.65)Cl_(0.36)Mg_(0.72)O_(2.52)Ti_(0.36) having a molecularweight of 203.46 g/mol.

Example 2

Step 1-2: Same as Example 1. Step 3: The reaction temperature was raisedto 150° C. and the stirring speed to 500 rpm. This condition wasmaintained for 1.5 hours followed by the collection of byproducts in theDean-Stark trap. Four extra additions of dehydrated n-butanol (4×25.0mL, 4×0.27 mol) were then introduced at flow rate of 15 mL/min every30min for an additional 4.0 hours of reaction time. Step 4: Same asExample 1.

Under the conditions of Example 2, the intermediate complex suspensionwas determined by ICP-OES to contain 0.314 M titanium and 0.618 Mmagnesium, which is a magnesium:titanium ratio of about 2.0. A combined58 mL of ethanol (39 mL) and n-butanol (19 mL) were removed via theDean-Stark trap. The intermediate complex of Example 2 is:

0.36TiCl(O-n-Bu)₃.0.72Mg(O-Et)_(1.1)(O-n-Bu)_(0.9).

The chemical formula isC_(8.50)H_(19.51)Cl_(0.36)Mg_(0.72)O_(2.52)Ti_(0.36) having a molecularweight of 209.35 g/mol. After collection of the solids and drying,ICP-OES analysis indicated that it contained 9.08 wt % Ti and 7.30 wt %Mg, with theoretical amounts of 8.20 and 8.33, respectively.

Example 3

Steps 1-4: Same as Example 1. The aim of this example is to reproducethe experiments on Example 1 and under these conditions reachconcentration of 0.3 M titanium and 0.6 M magnesium, which gives amagnesium: titanium ratio of about 2.0. A combined 21 mL of ethanol (17mL) and n-butanol (4 mL) were removed via the Dean-Stark trap. Theintermediate complex of Example 3 is:

0.36TiCl(O-n-Bu)₃.0.72 Mg(O-Et)_(1.6)(O-n-Bu)_(0.4).

The chemical formula isC_(7.78)H_(18.01)Cl_(0.36)Mg_(0.72)O_(2.52)Ti_(0.36) having a molecularweight of 199.27 g/mol. The FTIR spectra of the complex of Example 3 wasobtained suspended in hexane and in the isolated form. The spectra showcharacteristic α-C—H stretch vibrations bond to Mg and Ti suggesting theformation of the Ti—Mg complex.

Summary of Examples 1-3. The intermediate complex preparation includestwo main reaction steps, as shown in Scheme 1. Step 1 is an interchangereaction between titanium alkoxide and chloride to obtain a titaniumalkoxy-halide complex. Step 2 is a suspension of the magnesium ethoxideinto the titanium alkoxy-halide complex, which is promoted by thepartial or complete exchange reaction between butanol and magnesiumethoxide to form magnesium butoxide. After the formation of a uniform,suspended Ti—Mg complex, it is then allowed to suspend in excess ofhexane to reach concentrations of Ti lower than 0.4mol/L and thesuspension is maintained at 60° C. under stirring conditions for atleast 1 hour before being allowed to cool to 25° C.

The concentration of Ti and Mg after the addition of hexane wasestimated by ICP-OES. The Ti—Mg complex was suspended in approximately 2L of hexane (1^(st) dilution). The results are shown in Table 2.

TABLE 2 Metal concentration in the intermediate complex suspension inhexane by ICP-OES. Sample [Ti] mol/L [Mg] mol/L [Mg]/[Ti] Example 10.296 0.618 2.1 Example 2 0.314 0.618 2.0 Example 3 n.d. n.d. n.d. n.d.= not determined.

It is important to notice that the molar concentration ratio between[Mg]/[Ti] in the first dilution obtained by ICP-OES is 2.0, which is theexpected result as shown in the stoichiometric coefficients in Scheme 1.

The obtained suspensions were also analyzed by thermogravimetricanalysis (TGA), optical microscopy, Focused Beam Reflectance Measurement(FBRM), Dynamic Light Scattering (DLS), and Electrophoretic LightScattering (ELS).

TGA

Examples 1-3 were subjected to thermogravimetric analysis assuming thedecomposition product is titanium and magnesium oxide. Example 1 has atheoretical weight loss of 71.61 wt % and a measured weight loss of77.71 wt %. Example 2 has a theoretical weight loss of 72.49 wt % and ameasured weight loss of 72.98 wt %. Example 3 has a theoretical weightloss of 71.01 wt % and a measured weight loss of 76.88 wt %.

Optical Microscopy

The Ti—Mg complex suspensions (Example 1 and 2) were transferred to asample holder with a quartz window inside the glove box (under nitrogen)before the optical microscopy analysis. It has been observed that byincreasing the content of the butoxide group in Example 2 appears tosuppress the formation of aggregates in the micro-size range. Asreported by D. C. Bradley (Chem. Rev. 89, 1317-1322 (1989)), alkoxidescontaining less sterically bulky groups (e.g., methyl and ethyl) provedto be oligomers (e.g., dimers, trimers, and tetramers) due to thebridging propensity of the alkoxide group, which may be bounded throughits oxygen to two or three metals by means of conventional two-electroncovalent bonds. Therefore, by increasing the bulkiness of the alkoxidegroup in Example 2 (higher content of butoxide over ethoxide), it seemsto suppress the formation of large aggregates efficiently.

FBRM

The FBRM experiment is described by Yu, Z. Q. et al. Organic ProcessResearch & Development 2008, 12, 646:

-   -   In Focused Beam Reflectance Measurement (FBRM), a focused laser        beam spinning at high speed propagates into slurry/suspension        through a sapphire window mounted on the tip of a cylindrical        probe. When the laser beam intersects the edge of a particle,        some of it is backscattered to the detector installed in the        same probe, and induces a rise signal in the circuit until it        reaches the opposite edge of the particle. A chord length is        thus registered. The product of risetime and tangential velocity        of the spinning laser beam is a chord length. The measurement        range of a chord length depends on the scanning speed of the        laser beam and is divided into a fixed number of linear channels        in the hardware. Each count of chord length is recorded in a        corresponding channel and a chord length distribution (CLD) is        thus generated. Chord length counts grouped by channels are the        primary data provided by FBRM. In addition, the control        interface provides a variety of weighted or unweighted        statistics of the primary data, e.g. total counts of chord        lengths in all channels, mean chord lengths, median standard        deviation of CLD, etc., which are different statistical        presentations of the primary data.

For the FBRM measurement conducted here, 1 L jacketed reactor equippedwith an overhead stirrer and a portable FBRM® G600B from Mettler-Toledowas used. The FBRM® is a real-time quantitative measurement that tracksthe rate and degree of change to particles, particle structures, anddroplets in a medium. The G600B wetted probe dimensions (D×L) are 19mm×400mm built with a Hastelloy C22 and Sapphire window. The probetemperature operation range is −10° C. to 120° C. and a pressure limitof 10 bar. The intermediated complex suspension is transferred to thereactor and further diluted with hexane to reach a [Ti] of 0.125 mol/L.The mixture was then stirred at 250 rpm for 30 min at 30° C. prior tothe measurement. The stirring was stopped, and the cord length of theparticles of the material of Example 1 suspended domains in hexane wasrecorded as shown in FIG. 3. FIG. 4 illustrates that the suspension isstable over time at 30° C. and 40° C. without stirring.

The Ti—Mg complex suspensions were transferred to a sample holder with aquartz window inside the glove box (under nitrogen) for opticalmicroscopy analysis.

DLS

All Dynamic Light Scattering (DLS) measurements were carried out in aZetasizer NANO from Malvern Instruments using a quartz cell for themeasurements. All the samples were prepared under an inert atmosphere,and the cell was capped during the measurement.

FIG. 5 is an illustration of the size distribution by intensity andvolume of the Examples 1-3 suspension in hexane at 25° C. and [Ti] of0.125 mol/L. Under this condition the samples showed a bimodal particlesize by intensity distribution in the ranges shown in Table 3.

TABLE 3 Summary of DLS results of the material of Examples 1-3 as asuspension in hexane at [Ti] = 0.125 mol/L and 25° C. Examples Peak^(a),nm (Intensity, %) 1 2.33 (8.7); 294.3 (96.3) 2 2.70 (3.9); 396.0 (21.9)3 2.33 (15.6); 122.0 (57.0)  ^(a)sizes are given in diameter

ELS

All of the Electrophoretic Light Scattering (ELS) measurements werecarried out in a Zetasizer NANO from Malvern Instruments using a solventresistance cell in a quartz cuvette.

TABLE 4 Summary of ELS results of the material of Example 1 and 3 as asuspension in hexane at [Ti] = 0.125 mol/L. Examples Zeta Potential (mV)Mobility (μmcm/V · s) 1  −9.94 −0.03697 2 n.d. n.d. 3 −20.3 −0.07530Measurement duration from 10-100 runs at 25° C. using hexane as adispersant. The hexane refractive index is 1.390, viscosity 0.3 cP, anddielectric constant is 1.89.

Example 4

To a 1 L glass reactor equipped with a mechanical agitator, heatedjacket, and reflux condenser under an inert atmosphere, 336 mL of theintermediate complex of Example 1 in hexane ([Ti]=0.296 mol/L) wasadded. The stirrer was set to 1500 rpm and the reactor temperature to30° C. Under these conditions, 280.0 mL of ethyl aluminum sesquichloride(EASC) solution (50wt % in hexane (0.47 mol)) was added at a flow rateof 5.00 mL/min. The obtained slurry mixture is then allowed to heat upto 60° C., and the reactive mixture is kept at this condition for 1hour. Before starting the washing step, the reactor temperature wasreduced to 40° C. The agitation was stopped, and the solid pre-catalystwas allowed to settle at the bottom of the reactor. The supernatant wasremoved by cannula to a quench vessel, and 500 mL of hexane was added.The slurry was stirred at 300 rpm for at least 15 min, and the step wasrepeated at least three more times before the final pre-catalyst slurrywas transferred to a storage flask under an inert atmosphere. Theresults are shown in Table 5.

Example 5

Similar conditions of Example 4. The differences are: (a) IntermediateComplex of Example 1 in hexane [Ti]=0.205 mol/L to produce thepre-catalyst of this Example. The results are shown in Table 5.

Example 6

Similar conditions to Example 5 were used. However, the IntermediateComplex of Example 1 in hexane [Ti]=0.125 mol/L and a stirring speed of1700-1800 rpm were used to produce the pre-catalyst. The results areshown in Table 5.

Example 7

Similar conditions to Example 6 were used. However, a stirring speed of1800 rpm, a reaction temperature of 40° C., and an EASC flow rate of 1-2mL/min were used. The results are shown in Table 5.

Example 8

Similar conditions to Example 7 were used. However, the reactiontemperature was 30° C. The results are shown in Table 5.

Example 9

Similar conditions to Example 8 were used. However, the reactiontemperature was 60° C., and a stirring speed of 500 rpm was used. Theresults are shown in Table 5.

Example 10

Similar conditions to Example 8 were used. However the IntermediateComplex of Example 1 in hexane [Ti]=0.076 mol/L, a reaction temperatureof 30° C., a stirring speed of 1600 rpm, and a EASC volume of 140 mLwere used. The results are shown in Table 5.

Example 11

Similar conditions to Example 8 were used. However a stirring speed of1100 rpm was used. The results are shown in Table 5.

Example 12

Similar conditions to Example 10 were used. However the IntermediateComplex of Example 1 in hexane [Ti]=0.125 mol/L, a reaction temperatureof 10° C., and an EASC volume of 280 mL were used. The results are shownin Table 5.

Example 13

Similar conditions to Example 12 were used. However the IntermediateComplex of Example 1 in hexane [Ti]=0.076 mol/L, a reaction temperatureof −10° C., and an EASC volume of 140 mL were used. The results areshown in Table 5. FIG. 13 illustrates the particle size distributionmeasured in a Mastersizer 2000 laser diffraction particle size analyzerfrom Malvern Panalytical, for Examples 7, 11, and 12.

Note that in each of Examples 4-14, a setup as illustrated in FIG. 10Awas used.

TABLE 5 Summary of pre-catalyst synthesis conditions using feedingmethod A. Ti-Mg complex Stirring EASC^(d) suspension Speed T Volume Flowrate —Cl/-OR Pre-catalyst (mol_(Ti)/L)^(a) (rpm) (° C.)^(c) (L) (ml/min)mol/mol 4 0.293 1500 30 0.28 5 2.9 5 0.205 1500 30 0.28 5 3.7 6 0.1251700-1800^(b) 30 0.23 5 5.0 7 0.125 1800 40 0.23 1-2^(e) 5.0 8 0.1251800 30 0.23 1-2^(e) 5.0 9 0.125  500 60 0.23 1-2^(e) 5.0 10 0.076 160030 0.14 1-2^(e) 5.0 11 0.125 1100 30 0.23 1-2^(e) 5.0 12 0.125 1600 100.23 1-2^(e) 5.0 13 0.076 1600 −10 0.14 1-2^(e) 5.0 ^(a)Ti-Mg complexsuspension volume used in the preparation of pre-catalysts 4-6 was 0.335L, and pre-catalysts 7-14 was 0.37 L; ^(b)stirring speed was increasedafter 35 min of reaction relative to the start of EASC transfer;^(c)temperature during the addition of EASC; ^(d)50 wt % solution inhexane; ^(e)flow rate increased after 80 min of reaction relative to thestart of EASC transfer.

Example 14

275 mL of hexane was transferred to 1 L glass reactor equipped with amechanical agitator, heated jacket, and reflux condenser under an inertatmosphere. The stirrer was set to 1600 rpm and the reactor temperatureto 30° C. Under these conditions was fed to the reactor simultaneously95 mL of the Intermediate Complex of Example 1 in hexane ([Ti]=0.296mol/L) at 1.35 mL/min and 140.0 mL of ethyl aluminum sesquichloride(EASC) solution (50 wt % in hexane (0.235 mol)) at flow rate of 2.00mL/min. The obtained slurry mixture is then allowed to heat up to 60°C., and the reactive mixture was kept at this condition for 1 hour.Before starting the washing step, the reactor temperature was reduced to40° C. The agitation was stopped, and the solid pre-catalyst was allowedto settle at the bottom of the reactor. The supernatant was removed bycannula to a quench vessel, and 500 mL of hexane was added. The slurrywas stirred at 300 rpm for at least 15 min, and the step was repeated atleast three more times before the final pre-catalyst slurry wastransferred to a storage flask under an inert atmosphere. The resultsare shown in Table 6.

Example 15

Similar conditions to Example 14 were used. However the IntermediateComplex of Example 2 in hexane [Ti]=0.314 mol/L and stirring conditionof 1100 rpm were used. The results are shown in Table 6.

Example 16

Similar conditions to Example 15 were used. However the stirringcondition of 500 rpm was used. The results are shown in Table 6.

Example 17

Similar conditions to Example 15 were used. However the stirringcondition of 1500 rpm was used. The results are shown in Table 6.

Example 18

Similar conditions to Example 15 were used. However the stirringcondition of 1600 rpm was used. The results are shown in Table 6.

Example 19

Similar conditions to Example 18 were used. However the reactiontemperature of −10° C. was used. The results are shown in Table 6.

Example 20

Similar conditions to Example 18 were used. However the reactiontemperature of 60° C. was used. The results are shown in Table 6.

Therefore, two different methods for pre-catalyst preparation wereexplored in the examples above. Examples 4-14 use the addition of thehalogenated compound (EASC) into the Ti—Mg suspension, as shown in FIG.10A. Differently, examples 14-20 use the co-addition of the halogenatedcompound (EASC) and Ti—Mg complex suspension into a specific volume ofhexane to enable mixing conditions, as shown in FIG. 10B. Note that bythe pre-catalyst preparation method B (co-addition), the concentrationof Ti derived from the Ti—Mg complex is rapidly consumed over thereaction time, as exemplified in FIG. 7. As a result of this approach, amore pronounced dilution effect to the pre-catalyst particle sizeformation can be observed, as shown in FIG. 8.

TABLE 6 Summary of pre-catalyst synthesis conditions using feedingmethod B. Reactor Conditions IC EASC Stirring Flow Flow Hexane Speed T[Ti] Volume rate Volume rate Pre-catalyst (L) (rpm) (° C.) (mol/L) (L)(ml/min) (L) (ml/min) 14 0.275 1600 30 0.296 95 1.35 0.14 2.0 15 0.2751100 30 0.314 95 1.35 0.14 2.0 16 0.275 500 30 0.314 95 1.35 0.14 2.0 170.275 1500 30 0.314 95 1.35 0.14 2.0 18 0.275 1600 30 0.314 95 1.35 0.142.0 19 0.275 1600 −10 0.314 95 1.35 0.14 2.0 20 0.275 1600 60 0.314 951.35 0.14 2.0

Table 7illustrates is a summary of catalyst particle size andcomposition for Examples 4-20.

Chemical composition^(b) Pre-catalysts D₅₀ ^(a) (μm) Mg (wt %) Ti (wt %)Al (wt %) 4 8.9 7.5 7.3 2.6 5 10.6 6.7 6.2 2.2 6 7.8 8.7 6.3 3.0 7 8.913.0 13.6 4.6 8 8.0 9.2 11.3 4.0 9 21.9 10.0 8.4 4.6 10 7.5 10.5 11.14.4 11 14.4 9.3 10.2 3.5 12 6.7 8.3 9.3 3.6 13 4.5 11.1 10.2 5.0 14 4.012.2 13.8 3.9 15 5.9 10.5 16.9 3.9 16 7.9 9.3 11.6 2.8 17 4.8 7.4 11.62.9 18 3.7 10.0 11.7 3.5 19 5.3 9.3 10.1 3.7 20 3.2 10.2 12.4 3.9^(a)Off-line particle size measurement carried out by small-angle staticscattering (SASLS) in a Mastersizer ® 2000 (Malvern). ^(b)Determined byICP-OES from a dried pre-catalyst powder.

This is also a significant benefit to producing small particle sizepre-catalysts by using the pre-catalyst preparation method B (FIG. 10B)over the pre-catalyst preparation method A (FIG. 10A). As shown in FIG.11, the smaller pre-catalyst particle size range was obtained undersimilar shear rate conditions independently of the intermediate complexused in the Example 14-20 (pre-catalyst preparation method B). In otherwords, much less energy input was required to produce smallerpre-catalyst particle size in the pre-catalyst preparation method B(FIG. 10B).

Example 21

Ethylene polymerization was performed in a one-gallon reactor. Thereactor was purged at 100° C. under nitrogen for one hour. At roomtemperature, the reactor is charged with 2.3 L of hexane and 230 mg ofDEAC (diethyl aluminum). Then, 30 mg of pre-catalyst in hexane slurry isadded into the reactor. The reactor temperature was increased to 80° C.and then charged with ethylene to reach 120 psi. The pressure is keptconstant with ethylene pressure until 360 g of ethylene is consumed. Atthe end of the hold, the reactor was vented, and the polymer wasrecovered. The results are listed in Tables 8 and 9.

TABLE 8 Summary of the catalyst performance. Polymerization timePre-catalyst^(a) Yield CE^(c) Catalyst (min) (mg) (g) (kg_(PE) · g_(Cat)⁻¹ · h⁻¹) 4 64 30^(a) 346 11 5 59 30^(a) 350 12 6 71 30^(a) 349 10 7 9430^(a) 317 7 8 132 30^(a) 313 5 9 68 30^(a) 330 10 10 87 25^(b) 346 1011 88 26^(b) 307 8 12 86 31^(b) 329 7 13 60 20^(b) 181 9 14 120 16^(b)285 9 15 136 30^(a) 248 4 16 142 30^(a) 124 2 17 60 30^(a) 377 12 18 6030^(a) 402 13 19 60 30^(a) 124 4 20 60 30^(a) 257 10 ^(a)Experimentalpre-catalyst amount is 30 mg; ^(b)Determined by ICP-OES; ^(c)CE is anabbreviation for Catalyst Efficiency in units of (kg of polymer)/gpre-catalyst/hour).

TABLE 9 Polymer properties Polymers from above using the BD IV MW D₅₀materials of Catalyst (g/cm³) (dl/g) (10⁻⁶ g/mol) (μm) 4 0.391 26.1 6.92179.0 5 0.339  6.4 0.86 227.9 6 0.351 15.6 3.22 208.0 7 0.423 29.9 8.50226.0 8 0.402 26.6 7.14 196.2 9 0.320 22.2 5.46 582.6 10 0.376 24.8 6.44177.0 11 0.379 24.6 6.34 293.3 12 0.405 24.3 6.22 149.0 13 0.311 18.84.25 119.0 14 0.312 23.1 5.76 119.0 15 0.263 20.5 4.83 122.5 16 0.29729.0 8.11 n.d. 17 0.227 n.d. n.d. 111.0 18 0.307 21.1 5.03 107.0 190.230 23.1 5.79  79.5 20 0.193 n.d. n.d. n.d. ^(a)Intrinsic viscositymeasurements as described in ASTM D-4020. ^(b)Viscosity molecular weightwas estimated from Margolies equation, which is based on Mark-Houwinkparameters for polymer-solvent systems.

Example 22

Polymerization reactions were carried under similar conditions toExample 21. However, polymerization time was fixed to 30 min, andpre-catalyst systems underwent different activation conditions, as shownin Table 10. In this case, the polymerization reactor was charged withdifferent levels of DEAC, TiBA, and the mixture of both co-catalystsunder different molar ratio. The results are also summarized in FIG.12A-B.

TABLE 10 Summary of polymerization conditions, catalyst performanceresults, and polymer properties. Co-catalyst Co-catalyst CE^(c) BD, MW,D₅₀, Pre-catalyst^(a) Type (mmol) (kg_(PE) · g_(Cat) ⁻¹ · h⁻¹) (g/cm³)(10⁻⁶ g/mol) (μm) 12 DEAC 2.8 12.40 0.317 5.29 88 3.8 13.33 0.296 4.6788 4.8 13.33 0.306 4.65 92 12 TiBA 1.5 13.53 0.271 4.04 104 2.1 13.070.282 4.21 98 2.7 12.80 0.276 3.71 98 13 DEAC 2.8 13.07 0.256 5.45 1033.8 8.60 0.235 5.80 111 4.8 13.33 0.266 5.13 106 13 TiBA 1.5 12.87 0.2723.67 106 2.1 13.47 0.262 3.60 105 2.7 13.20 0.246 3.45 107 12 DEAC/TiBA2.2/0.6 12.97 0.280 4.85 98 1.4/1.4 13.06 0.285 5.95 94 0.6/2.2 14.110.270 4.63 102 13 DEAC/TiBA 2.2/0.6 13.07 0.261 3.45 89 1.4/1.4 13.600.268 3.98 113 0.6/2.2 12.93 0.276 4.97 97 ^(a)Target pre-catalyst feedwas 30 mg.

Example 23

A general polymerization procedure was carried out in a reactor cellwith a geometric volume of approximately 23 mL and a working volume ofapproximately 5.5 mL for the liquid phase equipped with a magneticallycoupled mechanical stirrer. The cell was initially purged underintermittent nitrogen flow at 90° C. to 140° C. for 8 hours. After thencooling to room temperature, the cell was fitted with disposable 10 mLglass and stir paddles, and the stir tops were then set back in thereactor system. The amount of dried heptane and 1-butene as co-monomerwas then fed through a syringe pump to the reactor system with thepresence of small amounts of alkyl aluminum as a scavenger. The systemwas then allowed to reach the set temperature and operating pressurewith ethylene, which general working pressure was 120 psi. Under thiscondition, using a slurry needle system, the amount of pre-catalystdispersed in heptane slurry (approx. 0.1 mg) was collected. A solutionof alkyl aluminum, usually the same used as a scavenger, in heptane wascharged to the needle system before being injected into the cell. Thepolymerization reaction starts under constant pressure by feedingethylene and stirring (800 rpm), typically for 30 min. The reaction wasquenched by over-pressurizing the system with dry air, and the reactorwas cooled to room temperature and vented. The glass cell was removedfrom the reactor, the solvent evaporated in a centrifugal evaporator,and the obtained polymer dried under vacuum overnight.

The polymerization results are summarized in Table 11 for the testedcatalyst system.

TABLE 11 Summary of polymerization conditions. 1-Butene CE^(c)Pre-catalyst^(a) Co-catalyst Type (mmol) (kg_(PE) · g_(Cat) ⁻¹ · h⁻¹) 12DEAC 0.5 10.4 1.1 11.3 1.6 11.3 12 TiBA 0.6 28.1 1.1 9.7 1.6 6.2 13 DEAC0.5 13.0 1.1 10.5 1.6 5.8 13 TiBA 0.5 25.2 1.1 9.6 1.6 3.0 14 DEAC 0.58.7 1.1 5.4 1.6 2.8 14 TiBA 0.5 19.4 1.1 14.0 1.6 18.8

Example 24

The effect of temperature and mixing on particle size was studied. Asshown in FIG. 14, three different operations are described. It has beenfound that differences in the mechanisms of pre-catalyst formation,feeding methods B and C have a very distinguished temperature responseto pre-catalyst particle size compared to method A. It has been foundthat the pre-catalyst particle size is decreased by increasing thetemperature of the medium when reactants feeding methods B and C areused, as shown in FIG. 15. The preparation conditions of thepre-catalysts system under different reaction temperature is summarizedin Table 12.

TABLE 12 Summary of the pre-catalyst preparation examples underdifferent methods. IC Suspension EASC [Ti], Volume, Flow rate, T,Volume, Flow rate, Method^(a) Examples mol/L L mL/min ° C. L mL/minMethod B^(b) 18 0.314 0.095 1.35 30 0.14 2.0 25 0.314 0.095 1.35 −100.14 2.0 26 0.314 0.095 1.35 60 0.14 2.0 Method C 27 0.314 0.095 1.0 300.415 n.a. 28 n.d. 0.095 1.0 30 0.415 n.a. 29 n.d. 0.095 1.0 60 0.415n.a. 30 n.d. 0.095 1.0 −10 0.415 n.a. 31 n.d 0.095 1.0 −10 0.415 n.a.^(a)All examples were carried out at stirring speed of 1600 rpm; ^(b)275mL of hexane was used as an inert medium for the co-addition; ^(c)flowrate increased after 80 min of reaction relative to the start of EASCaddition.

TABLE 13 Summary of pre-catalyst particle size and metal compositionFeeding Mode Chemical composition method Pre-Catalyst (μm)^(a,b) Mg (wt%) Ti (wt %) Al (wt %) Method B 18 3.8 10.0 11.7 3.5 25 5.5 9.3 10.1 3.726 3.3 10.2 12.4 3.9 Method C 27 5.5 9.3 11.5 3.7 28 5.5 n.d n.d. n.d.^(a)Off-line particle size measurement carried out by small-angle staticscattering (SASLS) in a Mastersizer ® 2000 (Malvern). ^(b)Mode refers tothe highest peak seen in the distribution and used in these cases due tothe multimodality of the distributions in Method C. ^(c)Determined byICP-OES from a dried pre-catalyst powder

Method A. To a 1 L glass reactor equipped with a mechanical agitator,heated jacket, and reflux condenser under an inert atmosphere, 375 mL ofthe intermediate complex suspension in hexane ([Ti]˜0.3 mol/L) is added.At mixing speed of 1600 rpm the desired temperature is set from −10° C.to 60° C. Under these conditions, 230.0 mL of EASC 50 wt % in hexane isadded at 1.0-2.0 mL/min. The obtained pre-catalyst slurry is thenallowed to heat up to 60° C., and the reactive mixture is kept at thiscondition for 1 hour. Before starting the washing step, the reactortemperature is reduced to 40° C. The agitation was stopped, and thesolid pre-catalyst is allowed to settle at the bottom of the reactor.The supernatant is removed by cannula to a quench vessel, and 500 mL ofhexane is added. The slurry is stirred at 300 rpm for at least 15 min,and the step is repeated at least three more times before the finalpre-catalyst slurry is transferred to a storage flask under an inertatmosphere.

Method B. Hexane (275 mL) was transferred to 1 L glass reactor equippedwith a mechanical agitator, heated jacket, and reflux condenser under aninert atmosphere. At stirring speed of 1600 rpm the desired temperatureis set from −10° C. to 60° C. Under these conditions, 95 mL of theintermediate complex suspension in hexane ([Ti]˜0.3 mol/L) at 1.35mL/min and 140.0 mL of EASC 50 wt % in hexane at a flow rate of 2.00mL/min are fed to the reactor, simultaneously. The obtained slurrymixture is then allowed to heat up to 60° C., and the reactive mixtureis kept at this condition for 1 hour. Before starting the washing step,the reactor temperature was reduced to 40° C. The agitation was stopped,and the solid pre-catalyst is allowed to settle at the bottom of thereactor. The supernatant is removed by cannula to a quench vessel, and500 mL of hexane is added. The slurry is stirred at 300 rpm for at least15 min, and the step is repeated at least three more times before thefinal pre-catalyst slurry is transferred to a storage flask under aninert atmosphere.

Method C. To a 1 L glass reactor equipped with a mechanical agitator,heated jacket, and reflux condenser under an inert atmosphere, 415 mL ofthe EASC 19 wt % solution in hexane is added at room temperature. Thestirring speed of 1600 rpm and reactor temperature from −10° C. to 60°C. is then set. Under these conditions, 90.0 mL of intermediate complexsuspension in hexane ([Ti]˜0.3 mol/L) is added at flow rate of 1.00mL/min. The obtained pre-catalyst slurry is then allowed to heat up to60° C., and the reactive mixture is kept at this condition for 1 hour.Before starting the washing step, the reactor temperature is reduced to40° C. The agitation was stopped, and the solid pre-catalyst is allowedto settle at the bottom of the reactor. The supernatant is removed bycannula to a quench vessel, and 500 mL of hexane is added. The slurry isstirred at 300 rpm for at least 15 min, and the step is repeated atleast three more times before the final pre-catalyst slurry istransferred to a storage flask under an inert atmosphere.

Particle formation over the course of the pre-catalyst synthesis wasmonitored using a ParticleView V19 from Metller-Toledo. This probeenabled an image-based monitoring of the particle formation and trackschange in turbidity image analysis as a function of image brightness andthe intensity of the light source. The turbidity image analysis profilesof the pre-catalyst synthesis as a function of the reaction temperatureusing reactants feeding Method C is shown in FIG. 16. In theseexperiments, the turbidity unity (TU) from the image analysis is afunction of particle size and solid concentration, which is changed bythe temperature of the reaction medium. Other important parameters, suchas particle shape, particle brightness, refractive index, and allreaction process parameters (i.e., stirring speed, feed rate, theconcentration of the reactants and source of reactants) are kept thesame among the selected experiments.

In a different embodiment, the Turbidity Unity (TU) relative to theimage analysis obtained from PVM V19 probe was modeled using equation(2), where k_(T)(T) is the TU time constant and is a function of reactoroperating temperature, and TU_(max)(T) is the maximum TU for the system,and it is also a function of reactor temperature, as shown in FIG. 17.Equation (2) reflects the onset of change in turbidity in the reactivemedium to the completion of the IC feeding in the pre-catalystpreparation Method C.

$\begin{matrix}{\frac{dTU}{dt} = {{k_{T}(T)}\left( {{T{U_{\max}(T)}} - {TU}} \right)}} & {{Equation}\mspace{14mu} (2)}\end{matrix}$

The values for k_(T) and TU_(max) for each experimental run weredetermined by formulating and solving a nonlinear programming problem(NLP) where the objective is to minimize the mean squared error betweenmeasured and calculated TU vales. Equation (2) was integrated in time bymeans of orthogonal collocation on finite elements using threeLagrange-Radau collocation points, and the temperature was assumed to beconstant for each experimental run. The NLP is represented in equation(3), and it was implemented in Pyomo and solved using IPOPT 3.12.13. Thevalues for k_(T) and TU_(max) are presented in Table 1 at each.

$\begin{matrix}{{\min\limits_{k_{T},{TU}_{\max}}{\sum_{k}^{NFE}{{{TU}_{(k)} - {TU}_{(k)}^{*}}}^{2}}}{{s.t.\mspace{11mu} {TU}_{({k + 1})}} = {f\left( {{TU}_{(k)},T} \right)}}} & {{Equation}\mspace{14mu} (3)}\end{matrix}$

TABLE 14 Model Parameters at different temperatures Pre-catalystsReaction Temperature k_(T), 1/hour TU_(max) ^(a) 30 −10° C. 2.121540120.5942200306 28 30° C. 2.49112764 0.7696509401 29 60° C. 3.145700160.8655988585 ^(a)turbidity units relative to image analysis obtainedfrom PVM V19 probe.

The functions k_(T)(T) and TU_(max)(T) are defined by the second orderpolynomial defined by equation (4) and equation (5):

k _(T)(T)=0.0001797*T ²+0.005646*T+2.16   Equation (4)

TU_(max)(T)=−1.696e−05*T ²+0.004725*T+0.6432   Equation (5)

Example 32

Same initial workup procedure as Example 23, but in these experiments,the amount of dried heptane was initially fed through a syringe pump tothe reactor system with the presence of 1.0 μmol of DEAC as a scavenger.The system was then allowed to reach the set temperature (from 65-100°C.) and operating pressure with hydrogen and ethylene, which generalworking pressure ranged from 110-135 psi. Under this condition, using aslurry needle system, the amount of pre-catalyst dispersed in heptaneslurry (approx. 0.03 mg) was collected. A solution containing 3.6 μmolof DEAC in heptane was charged to the needle system before beinginjected into the cell. The polymerization reaction starts underconstant pressure by feeding ethylene and stirring (800 rpm), typicallyfor no longer than 60 min. The reaction was quenched byover-pressurizing the system with dry air, and the reactor was cooled toroom temperature and vented. The glass cell was removed from thereactor, the solvent evaporated in a centrifugal evaporator, and theobtained polymer dried under vacuum overnight.

TABLE 15 Summary of polymerization conditions Run, Temperature, P_(C) ₂_(H) ₄, P_(H) ₂ , CE, kg_(PE) · Pre-catalyst^(a) # ° C. psi psi g_(Cat)⁻¹ · h⁻¹ 18 P1 65 105 5 9.4/9.5 P2 100 10 8.6/5.5 P3 90 20 6.0/6.3 18 P475 105 10 13.6/13.7 P5 95 20 11.2/6.7  P6 75 40 6.1/5.7 18 P7 85 115 1015.5/18.4 P8 105 20 13.7/14.5 P9 85 40 7.9/7.9 18 P10 100 125 1014.1/14.6 P11 115 20 11.0/7.5  P12 95 40 8.2/8.0 13 P13 65 105 5 6.8/8.2P14 100 10 6.3/6.0 P15 90 20 5.1/5.2 13 P16 75 105 10 4.7/6.9 P17 95 207.2/7.0 P18 75 40 3.6/3.7 13 P19 85 115 10  8.0/17.3 P20 105 20 5.3/12.8 P21 85 40 7.5/7.7 13 P22 100 125 10  5.4/11.1 P23 115 2011.4/7.7  P24 95 40 8.0/8.0 30 P25 65 105 5 4.3/4.5 P26 100 10 3.5/3.6P27 90 20 3.2/3.5 30 P28 75 105 10 4.0/4.3 P29 95 20 4.6/1.9 P30 75 402.8/2.8 30 P31 85 115 10 8.5/6.4 P32 105 20 6.7/5.2 P33 85 40 3.8/4.1 30P34 100 125 10 12.9/8.2  P35 115 20 9.1/4.0 P36 95 40 3.8/3.2 ^(a)Feedin hexane slurry.

The polymerization results are summarized in Table 16 for the testedcatalyst system. The obtained polymers were then characterized by hightemperature size exclusion chromatography (HSEC) and crystallizationelution fractionation (CEF).

TABLE 16 Summary of the obtained polymer properties. Run, HSEC CEFCatalyst # M_(n), kDa M_(w), kDa M_(w)/M_(n) X_(Tel<30° C.) ^(A), wt %X_(Tel>85° C.) ^(B), wt % 18 P1 197/229 1082/1029 5.5/4.5 0.1 97.4 P2n.d. n.d. n.d. n.d. n.d. P3 114/104 608/639 5.3/6.2 0.2 98.6 18 P4131/151 757/760 5.8/5.0 n.d. n.d. P5 79/88 488/541 6.2/6.1 0.1 99.7 P640/41 279/313 6.9/7.6 0.6 98.8 18 P7 98/102 669/608 6.9/6.0 <0.1 99.3 P866/91 411/476 6.2/5.2 0.4 99.2 P9 29/32 219/225 7.6/7.0 0.6 98.5 18 P1088/83 521/408 5.9/4.9 0.8 98.8 P11 63/33 255/185 4.1/5.6 0.7 98.9 P1234/39 164/151 4.8/3.9 0.9 98.4 13 P13 194/208 1197/1180 6.2/5.7 0.3 97.5P14 179/176 898/960 5.0/5.5 0.4 98.5 P15 125/98 699/682 5.6/6.9 0.3 98.013 P16 122/92 724/781 5.9/8.5 n.d. n.d. P17 87/89 521/525 6.0/5.9 0.299.2 P18 44/47 283/276 6.4/5.9 0.4 99.3 13 P19 117/109 678/533 5.8/4.90.8 97.8 P20 95/55 474/395 5.1/7.1 0.7 98.6 P21 34/36 234/238 6.9/6.50.9 97.9 13 P22 90/93 445/421 5.0/4.5 0.9 98.8 P23 59/75 268/321 4.6/4.30.6 99.1 P24 34/41 128/181 3.8/4.4 0.9 98.1 30 P25 133/125 773/6805.8/5.4 0.2 98.7 P26 105/83 595/700 5.7/8.4 0.2 98.9 P27 67/72 372/3915.5/5.4 0.3 99.0 30 P28 71/70 509/511 7.1/7.3 0.2 99.6 P29 52/43 276/2865.3/6.6 0.3 99.4 P30 37/31 164/169 4.5/5.4 0.6 98.7 30 P31 69/66 410/3495.9/5.2 0.4 99.4 P32 56/63 280/287 5.0/4.6 0.5 99.0 P33 28/33 193/1506.9/4.6 1.0 98.0 30 P34 71/64 347/306 4.9/4.8 0.6 98.9 P35 41/44 209/2375.2/5.4 0.6 98.6 P36 19/29 112/132 5.8/4.6 2.1 96.2

Para. 1. A complex of Formula I:

XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I)

wherein: a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1;0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are eachindependently a linear or branched alkyl, a linear or branchedheteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substitutedheterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R² isnot the same as R³.

Para. 2. The complex of Para. 1, wherein R¹ is a C₃-C₆ alkyl, R² isC₂-C₄ alkyl, and R³ is a C₃-C₆ alkyl.

Para. 3. The complex of Para. 1 or 2, wherein R¹ is n-butyl, R² isethyl, and R³ is n-butyl.

Para. 4. The complex of any one of Paras. 1-3, wherein p is 1.

Para. The complex of any one of Paras. 1-4, wherein q is from about 0.5to 1.5, and t is from about 0.5 to 1.5.

Para. 6. The complex of any one of Paras. 1-5, wherein X is 0.2 to 0.5and Y is 0.6 to 0.8.

Para. 7. The complex of any one of Paras. 1-6, wherein the molar ratioof X:Y is from 1 to 3.

Para. 8. The complex of any one of Paras. 1-7, wherein the molar ratioof X:Y is about 2.

Para. 9. The complex of any one of Paras. 1-8 that exhibits a ¹³C NMRspectra having an alkoxide resonance from 50 ppm to 80 ppm versusresidual solvent signal of deuterated toluene-d₈.

Para. 10. The complex of any one of Paras. 1-9 that exhibits a ¹³C NMRspectra having an aryloxide resonance from 40 ppm to 120 ppm versusresidual solvent signal of deuterated toluene-d₈.

Para. 11. The complex of any one of Paras. 1-10, wherein weight residueobtained by thermal gravimetric analysis (TGA) is from 20 wt % to 35 wt%.

Para. 12. The complex of any one of Paras. 1-11, which exhibits aFourier Transform Infrared C—H stretching vibration at a wavenumber from2500 cm⁻¹ to 4000 cm⁻¹.

Para. 13. A colloidal suspension comprising an organic solvent and acomplex of Formula I:

XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I)

wherein: a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1;0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are eachindependently a linear or branched alkyl, a linear or branchedheteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substitutedheterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R² isnot the same as R³.

Para. 14. The colloidal suspension of Para. 13, wherein the organicsolvent comprises an alkane, aromatic, or a mixture of any two or morethereof.

Para. 15. The colloidal suspension of Para. 13 or 14, wherein theorganic solvent comprises n-hexane, n-pentane, cyclohexane, toluene,benzene, benzine, o-cresol, p-cresol, m-cresol, 1,2-dimethylbenzene,1,3-dimethylbenzene, 1,4-dimethylbenzene, ethylbenzene, cumine,trichloroethylene, trichlorobenzene, o-dichlorobenzene, or a mixture ofany two or more thereof.

Para. 16. The colloidal suspension of any one of Paras. 13-15, whereinthe complex exhibits a multimodal domain size of a dispersed phase.

Para. 17. The colloidal suspension of Para. 16, wherein theconcentration of the Ti and Mg is from 1×10⁻⁵M to 2.0 M, as determinedby inductively coupled plasma-optical emission spectrometry (ICP-OES).

Para. 18. The colloidal suspension of Para. 16 or 17, wherein themultimodal domain size exhibits a first peak with a domain size meanfrom 1 nm to 10 nm in diameter, and a second peak with a domain sizemean from 250 nm to 350 nm in diameter at 20° C.

Para. 19. The colloidal suspension of Para. 16, 17, or 18, wherein themultimodal domain size exhibits a first peak with a domain size meanfrom 250 nm to 400 nm in diameter, and a second peak with a domain sizemean from 4000 nm to 6000 nm in diameter at 50° C.

Para. 20. The colloidal suspension of Para. 16, 17, 18, or 19, whereinthe multimodal domain size exhibits a first peak when measured by FocusBeam Reflectance Measurement (FBRM) with a cord length mean from 1 μm to10 μm, when measured from −30° C. to 60° C.

Para. 21. A solid pre-catalyst system comprising solid particles of acomposite of a reaction product of a halogenated compound and acolloidal suspension of a complex of Formula I:

XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I)

wherein: a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1;0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are eachindependently a linear or branched alkyl, a linear or branchedheteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substitutedheterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R² isnot the same as R³.

Para. 22. The solid pre-catalyst system of Para. 21, wherein thehalogenated compound comprises diethyl aluminum chloride (DEAC),ethylaluminum sesquichloride (EASC), ethyl aluminum dichloride (EADC),titanium tetrachloride (TiCl₄), silicon tetrachloride (SiCl₄) or amixture of any two or more thereof.

Para. 23. The solid pre-catalyst system of Para. 21 or 22, wherein theTi is present from 0.5 wt % to 30 wt %.

Para. 24. The solid pre-catalyst system of any one of Paras. 21-23,wherein the Mg is present from 1 wt % to 20 wt %.

Para. 25. The solid pre-catalyst system of any one of Paras. 21-24,wherein the Al is present from 1 wt % to 20 wt %.

Para. 26. The solid pre-catalyst system of any one of Paras. 21-25,wherein the solid particles exhibit a D₅₀ from 1 μm to 30 μm.

Para. 27. The solid pre-catalyst system of any one of Paras. 21-26further contacting with a reducing agent.

Para. 28. A method of polymerizing or co-polymerizing an olefin monomer,the method comprising: contacting a solid pre-catalyst system comprisingsolid particles of a composite of a reaction product of a halogenatedcompound and a colloidal suspension of a complex of Formula I with areducing agent and the olefin monomer:

XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I)

wherein: a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1;0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are eachindependently a linear or branched alkyl, a linear or branchedheteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substitutedheterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R² isnot the same as R³.

Para. 29. The method of Para. 28, wherein the reducing agent comprisesdiethyl aluminum chloride (DEAC), triethyl aluminum (TEA), ethylaluminumsesquichloride (EASC), ethyl aluminum dichloride (EADC), triisobutylaluminum (TiBA), trimethyl aluminum (TMA), methylaluminoxane (MAO), or amixture of any two or more thereof.

Para. 30. The method of Para. 28 or 29, wherein the olefin monomercomprises ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene,1-octene, or a mixture of any two or more thereof.

Para. 31. The method of any one of Paras. 28-30, wherein the solidcatalyst system exhibits a catalyst efficiency (CE) of greater than 2kg_(PE)·g_(Cat) ⁻¹·h⁻¹.

Para. 32. The method of any one of Paras. 28-31, wherein the olefin isethylene, and the method further comprises collecting polyethyleneexhibiting an intrinsic viscosity of greater than 1.0 dl/g.

Para. 33. A method of forming a solid pre-catalyst system composition,the method comprising: contacting simultaneously a halogenated compoundand a colloidal suspension of a complex of Formula I into an inertliquid medium to form the solid pre-catalyst system:

XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I)

wherein: a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1;0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are eachindependently a linear or branched alkyl, a linear or branchedheteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substitutedheterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R² isnot the same as R³.

Para. 34. The method of Para. 33, wherein the organic solvent comprisesan alkane, aromatic, or a mixture of any two or more thereof.

Para. 35. The method of Para. 33 or 34, wherein the organic solventcomprises n-hexane, n-pentane, cyclohexane, toluene, benzene, benzine,o-cresol, p-cresol, m-cresol, 1,2-dimethylbenzene, 1,3-dimethylbenzene,1,4-dimethylbenzene, ethylbenzene, cumine, trichloroethylene,trichlorobenzene, o-dichlorobenzene, or a mixture of any two or morethereof.

Para. 36. The method of any one of Paras. 33-35, wherein the complex ofFormula I exhibits a multimodal domain size of a dispersed phase.

Para. 37. The method of any one of Paras. 33-36, wherein theconcentration of the Ti and Mg is from 1×10⁻⁵M to 2.0 M, as determinedby inductively coupled plasma-atomic emission spectrometry (ICP-OES).

Para. 38. The method of any one of Paras. 36-37, wherein the multimodaldomain size exhibits a first peak with a domain size mean from 250 nm to400 nm in diameter, and a second peak with a domain size mean from 4000nm to 6000 nm in diameter at 50° C.

Para. 39. The method of any one of Paras. 33-38, wherein the halogenatedcompound comprises diethyl aluminum chloride (DEAC), ethylaluminumsesquichloride (EASC), ethyl aluminum dichloride (EADC), titaniumtetrachloride (TiCl₄), silicon tetrachloride (SiCl₄) or a mixture of anytwo or more thereof.

Para. 40. The method of any one of Paras. 33-39, wherein the halogenatedcompound is diluted in an organic solvent at a concentration of greaterthan 5 wt %.

Para. 41. The method of any one of Paras. 33-40, wherein the inertliquid medium comprises an alkane, aromatic, or a mixture of any two ormore thereof.

Para. 42. The method of any one of Paras. 33-41, wherein the inertliquid medium comprises n-hexane, n-pentane, cyclohexane, toluene,benzene, benzine, o-cresol, p-cresol, m-cresol, 1,2-dimethylbenzene,1,3-dimethylbenzene, 1,4-dimethylbenzene, ethylbenzene, cumine,trichloroethylene, trichlorobenzene, o-dichlorobenzene, mineral oil, ora mixture of any two or more thereof.

Para. 43. The method of any one of Paras. 33-42, wherein a temperatureof the inert liquid medium is from −40° C. to +60° C.

Para. 44. The method of any one of Paras. 33-43, wherein the contactingcomprises stirring at 50 rpm to 1800 rpm.

Para. 45. The method of any one of Paras. 33-44, wherein the contactingcomprises simultaneous addition of the halogenated compound(s) and thecolloidal suspension of a complex of Formula I is at a constant chlorideto —OR^(x) molar ratio, where R^(x) corresponds to the collective R¹,R², and R³. 46. The method of any one of Paras. 33-45, wherein thechloride to —OR^(x) molar ratio is from 1 to 10.

Para. 47. The method of any one of Paras. 33-46, wherein the solidpre-catalyst system comprises Ti from 0.5 wt % to 30 wt %.

Para. 48. The method of any one of Paras. 33-47, wherein the solidpre-catalyst system comprises Mg from 1 wt % to 20 wt %.

Para. 49. The method of any one of Paras. 33-48, wherein the solidpre-catalyst system comprises Al from 1 wt % to 20 wt %.

Para. 50. The method of any one of Paras. 33-49, wherein the solidpre-catalyst system comprises pre-catalyst particles having a D₅₀ from 1μm to 15 μm.

Para. 51. The method of any one of Paras. 33-50, wherein the solidpre-catalyst system is further contacted with a reducing agent.

Para. 52. The method of Para. 51, wherein the reducing agent comprisesdiethyl aluminum chloride (DEAC), triethyl aluminum (TEA), ethylaluminumsesquichloride (EASC), ethyl aluminum dichloride (EADC), triisobutylaluminum (TiBA), trimethyl aluminum (TMA), methylaluminoxane (MAO), or amixture of any two or more thereof.

Para. 53. The method of any one of Paras. 33-52, wherein the solidcatalyst system is configured to polymerize, or co-polymerize, an olefinmonomer.

Para. 54. The method of any one of Paras. 33-53, wherein the olefinmonomer comprises ethylene, propylene, 1-butene, 4-methyl-1-pentene,1-hexene, 1-octene, or a mixture of any two or more thereof.

Para. 55. The method of any one of Paras. 33-54, wherein the solidcatalyst system exhibits an olefinic polymerization catalyst efficiency(CE) of greater than 2 kg_(PE)·g_(Cat) ⁻¹·h⁻¹.

Para. 56. The method of any one of Paras. 33-55, wherein the olefincomprises ethylene, the method further comprises collecting polyethyleneexhibiting an intrinsic viscosity of greater than 1.0 dl/g.

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications may be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms “comprising,” “including,” “containing,” etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited, and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application. Many modifications andvariations may be made without departing from its spirit and scope, aswill be apparent to those skilled in the art. Functionally equivalentmethods and compositions within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds, compositions, or biologicalsystems, which can of course vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range may be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein maybe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the like,include the number recited and refer to ranges which may be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember.

All publications, patent applications, issued patents, and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

Other embodiments are set forth in the following claims.

1. A method of preparing a solid pre-catalyst system comprising: in a reactor under agitation with a stirring mechanism, reacting a colloidal suspension of an organic solvent and a complex of Formula I with a halogenated compound or a mixture of halogenated compounds at a starting reactor temperature; allowing the mixture to exothermically react under a controlled feed rate to form a precipitate, which is then allowed to reach an upper temperature limit for a sufficient period of time; and allowing the mixture to cool to completion temperature; wherein: the complex of Formula I is: XTiCl_(p)(OR¹)₄.YMg(OR²)_(q)(OR³)_(t)   (I) a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1; 0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; R² is not the same as R³; and the precipitate exhibits a D₅₀ from about 3 μm to about 10 μm.
 2. The method of claim 1, wherein the complex of Formula I exhibits a Fourier Transform Infrared C—H stretching vibration bands at wavenumber from 2500 cm⁻¹ to 5000 cm⁻¹.
 3. The method of claim 1, wherein the starting reactor temperature is about −10° C. to about 60° C.
 4. The method of claim 1, wherein the upper temperature limit is less than about 70° C.
 5. The method of claim 4, wherein the upper temperature limit is about 60° C.
 6. The method of claim 1, wherein the completion temperature is about 35° C. to about 60° C. and the agitating comprises stirring the mixture at about 400 rpm to 2000 rpm.
 7. (canceled)
 8. The method of claim 1 further comprising collecting the precipitate and washing the precipitate with an organic solvent or a mixture of organic solvents comprising alkanes, aromatics, or a mixture of any two or more thereof.
 9. The method of claim 1, wherein the D₅₀ is from about 3 μm to about 12 μm.
 10. The method of claim 1, wherein the halogenated compound or a mixture of halogenated compounds comprises diethyl aluminum chloride (DEAC), ethylaluminum sesquichloride (EASC), ethyl aluminum dichloride (EADC), titanium tetrachloride (TiCl₄), silicon tetrachloride (SiCl₄) or a mixture of any two or more thereof. 11-12. (canceled)
 13. The method of claim 8, wherein organic solvent comprises n-hexane.
 14. The method of claim 1, wherein the reacting comprises charging the reactor with a first portion of the solvent and the halogenated compound or a mixture of halogenated compounds, and adding the complex of Formula I in a second portion of the solvent to the reactor at a first feed rate. 15-16. (canceled)
 17. The method of claim 1, wherein the reacting comprises charging the reactor with a first portion of the solvent and the complex of Formula I, and adding the halogenated compound or a mixture of halogenated compounds in a second portion of the solvent to the reactor at a first feed rate.
 18. The method of claim 17, wherein the first feed rate is from 0.05 mL/min to about 4.0 mL/min.
 19. The method of claim 17, wherein the starting temperature is from about −10° C., the upper temperature limit is about 60° C., and the sufficient time is about 1 hour, and the completion temperature is about 40° C. 20-21. (canceled)
 22. The method of claim 17, wherein the starting temperature is from about −10° C., the upper temperature limit is about 60° C., and the sufficient time is about 1 hour, and the completion temperature is about 40° C.
 23. The method of claim 14, wherein the parameters of turbidity of the reaction medium k_(T) ranges from 1.5 to 4.0 h⁻¹ and the maximum turbidity unity (TU_(max)) relative to image analysis range from 0.4 to 1.0 TU.
 24. A solid pre-catalyst system comprising solid particles of a reaction product of a complex of Formula I with a halogenated compound or a mixture of halogenated compounds; wherein: XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I) a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1; 0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; R² is not the same as R³; and the solid particles exhibit a D₅₀ from about 3 μm to about 12 μm. 25-26. (canceled)
 27. A method of polymerizing or co-polymerizing an olefin monomer, the method comprising: contacting a solid pre-catalyst system comprising solid particles of a composite of a reaction product of a halogenated compound and a colloidal suspension of a complex of Formula I with a reducing agent, optionally a chain transfer agent, and the olefin monomer or monomers: XTiCl_(p)(OR¹)_(4-p).YMg(OR²)_(q)(OR³)_(t)   (I) wherein: a molar ratio of X to Y (X/Y) is from 0.2 to 5.0; p is 0 or 1; 0<q<2; 0<t<2; the sum of q and t is 2; R¹, R², and R³ are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; R² is not the same as R³; and the solid particles exhibit a D₅₀ from about 3 μm to about 12 μm. 28-31. (canceled)
 32. The method of claim 27, wherein the olefin is ethylene, and the method further comprises collecting polyethylene exhibiting number average molar mass (M_(n)) between 10-250 kg/mol, or a weight average molar mass (M_(w)) between 150-1250 kg/mol, and wherein the polyethylene exhibits a polydispersity (M_(w)/M_(n)) from 3 and
 8. 33-34. (canceled)
 35. The method of claim 27, wherein the olefin is ethylene, and the method further comprises collecting polyethylene, and wherein less than 5 wt % of the polymer is eluted with 1,2-dichlorobenzene below 30° C. by crystallization elution fractionation (CEF) analysis.
 36. (canceled) 